Oxidizing phosphorus



April 24, 1945. G. L. FREAR OXIDIZING PHOS'PHORUS Filed Dec. 3o, 1940 5 Sheets-Sheet 1 INVENTOR PER CENT CONVERSION BY ATTORNEY April 24, 1945. G. l. FREAR 2,374,188

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PREFERENTML oxwATloN oF PHosPHQRus m fl BLAST FURNACE REDucnoN GAS 300 l I/ l/ 200 ,f u www@ A 2co+oz2c02 loo f f ,f 80 |00 f HG2 O 0 40 60 George L. Frear INVENTOR v PER CENT CONVERSION ATTORNEY April 24, 1945. G. l. FREAR oxIDIzING PHosPHoRus Filed DeC. 50, 1940 3 Sheets-Sheet 3 60 George L. F rer INVENTOR PER CENT CONVERSION ATTORNEY Patented Apr. 24, 1945 UNITED STATES PATENT OFFICE PHOSPHQRUS4 George Il. Frear, near Sheffield; Ala., assigner to Tennessee Valley Authoritya corporation of' the United Statesofr' America Application. December 30,1940, Serial No. 372,-,404

(Cl. 2k3-4651) (Granted under the act of March 3, 1883 as:v

amended Anrilf30, 1928.; 370:0; G1757 The invention herein described maybemanutfactured andusedby or fory the' Government for' governmental purposes without the payment to: me of any royalty thereon. i

Thisinvention relates to a process of oxidizing elemental phosphorus, particularlyl the preferential oxidation of' elemental' phosphorus inr gaseous mixtures containing carbonm'onoxid'e.

In the. oxidation of' elemental phosphorus` contained'in phosphate reduction furnace gasit has. become. customary' to oxidize all or atleast a substantial proportion ofthe carbon monoxide contained therein in order to completely'recover the phosphorus in its highest state of oxidation,. namely, as. phosphorus pentoxide. It has. long. been recognized as desirable to oxidize only the elemental phosphorus. in such. agaseous mixture. in order that. the carbon monoxide may he available for various uses in the. arts rather than to have it'v burned' with` the production of, heat under conditionssuch that the heat may notbe. readily utilized.

Consequently, it has. been proposed that only the elemental phosphorus ina phosphate. reduction furnace. gas. be. oxidized, andthe oxidized; phosphorus be removedtherefi'om with therecow ery of allloffthe carbon monoxidetherein.A Likewise, numerous. proposals have. .been made directed toward the. conzipl'eteoxidationof.l alllof' the,

elementalphosphorus andonl'y a part'. oi the. car- 30 bon monoxide. in sucha gasbut, asinthecaseof the first proposal referred` to above, none. ofi the. conditions necessary for eiecting thezcomplete oxidation of` the. elementalv phosphorus and.. thel minimum oxidation of the carbon monoxidehave 35 relevance to the complete oxidationfofphosphorus- 40' which is vat the same time. preferential. as far as. the oxidation of carbon monoxide associated therewithV isl concerned.

The principal object of the. presentA invention is to provide a methodlfor. the complete oxidation` of the. elemental phosphorus in aA gaseous mix ture containing elemental phosphorus and'v oar.- bon monoxide Without simultaneously oxidizing any substantial portiony of`V such carbonmonoxide. vide a. method for treatingV4 phosphate reduction. furnace gasW-herebythe` carbon monoxide there,- inv may beconserved. Other objects of thiswinvention include.. the: provision of. a. method`-` for Another object of` this invention isto-pro 50' ciated` with* carbon monoxide under conditions such'thatthe' phosphorus' pentoxide obtained'mayv bereadil'y' recovered:

I'A have discovered a process of preferentially oxidizing 'phosphorus in theA presence of substantiaIv proportions' of carbona monoxidev by forming.

a uniform gaseous' mixture of said elemental phosphorus and carbon' monoxide; with an OXY-A gerr-containinggasgqby'heating said, gaseous'mixture uniformlyto' a temperature* of the ordero- 500 C- and. maintaining said temperaturen for a sufficient' length; of; time to oxidize" substantially gen to producephosphorus pentoxide.- as a func.- tion of. temperaturathe. relationshipV for percent. carbon monoxide oxidized by oxygen; to. produce` carbon dioxide. asa. function of. temperaturlthe. relationship fon per. cent elementalphosphorusoxidized byr carbon dioxide-to lproduce:phosphorus` pentoxide as a function of teInperature;y and con.- versely' from. the4v latter, the relationship for; per cent. ofi phosphorus pen-toxde; reduced'bxry carbon monoxide as a function oftemperaturapwitlneach;

relationship-being an: approximati'ombased on iiiformation hitherto available;

Fig. 2: shows.respectively; the relationship for per cent; elemental phosphorus oxidized to. pro'- duce'; phosphoruspentoxide as at functionv ofr tem'- perature;` and;l the relationship' f'orfper'cent carkion'- monoxide oxidized* tocarbon dioxide as a function of' temperature when phosphate reduction furnaceega'ses; produced in anw electric furnace; are oxidized* byair admixed therewith.

Fig. 3* shows, respectively; the relationshipfor per` cent elemental phosphorus oxidized-1 to producephosphorus pentoxide as a functionoftem'- peratureandthe rel'ati'onship'fr 'per cent carbon monoxide oxidized' to" carbon dioxiden as" a. inction of temperature. when, phosphate reductiony The, ignitiontemperature. offphosphorus fin; air

the'oxid'ation4 of.- the4 elementaly phosphorus asso- 555 'SI.'BD0111e d(Mellor- C. Il C. 8,772.' (1931)) mixture of P203 and P205 corresponds to the oxidation of 50% of the phosphorus to P205. Taking the temperature of 175 C. midway between 60 and 290 C., it is assumed that the oxidation of phospho-rus at this temperature in a restricted supply of air would produce a yield of 50% of the phosphorus so oxidized as phosphorus pentoxide.

P203 also undergoes oxidation on heating at 440 C. yielding P204 as well as red phosphorus (Holleman and Cooper, Textbook of Inorganic Chemistry,. 210 (1916)). When heated in vair P204 is not oxidized rapidly until a temperature of 500 C. is approached (Emmett and Shultz, Ind. Eng. Chem.' 31, 105-111 (1939)). When only the theoretical amount of air to give P205 is used, there will be little oxygen available to complete the oxidation of all of the lower oxides of phosphorus t phosp'orus pentoxide at 500 C. Furthermore, the P205 of commerce is usually contaminated with lower oxides (Vanino, Preparative Chemie. 1, 194 (1927)). Hence, the oxidation of phosphorus to phosphorus pentoxide is represented as 95% complete at 500 C. Further heating in the presence of the theoretical amount of oxygen would not be expected to increase the oxidation of the lower oxides ofphosphorus to phosphorus pentoxide except insofar as the stability of the lower oxides in the system may be aifected by the temperature. y

Curve 2 represents the extent of oxidation of carbon monoxide by oxygen at various temperatures 'since' it is known that the oxidation of carbon monoxide starts very slowly at 600 C. and consumes all the free air remaining at,650 C., which is approximately the temperature at which carbon monoxide and oxygen react explosively (Semenoff, Chemical Kinetics and Chain Reactions, 264-79 (1935) Curve 3 represents the extent of oxidation of elemental phosphorus by carbon dioxide based on sourcematerial as follows: v

It has been found (Emmett and Shultz, Ind. Eng. Chem. 31, 105-111 (1939))` that elemental phosphorus is oxidized by carbon dioxide at a measurable rate at` 800 C. and that equilibrium is established rapidly at 1000 C. Their data show troxide (P204), 1 mol of phosphorus pentoxide (P205) 9 mols of carbon monoxide, and 18 mols of carbon dioxide. One-half of the 'original phosphorus in this mixture is oxidized completely to phosphorus pentoxide, whereas the other half of the phosphorus is oxidized to phosphorus tetroxide.

The reverse reaction, namely, the reduction of phosphorus pentoxide by carbon monoxide has been assumed to begin at 800 C. and such an assumption has been veried experimentally, In view of its relation in the consideration of the present invention the extent of reduction of phosphorus pentoxide by carbon monoxide as a function of temperature is represented in curve 4 as complementary to curve 3. Curve 4 starts at the same temperature as curve 3 and reaches the same equilibrium composition at 1000 C. The initial composition for this reduction reaction is 2 mols of phosphorus pentoxide (P205), 10 mols of carbon' monoxide, and 17 mols of carbon di-` oxide.

In Fig. 2, curve 5 shows the extent of oxidation of elemental phosphorus in phosphate reduction furnace gas, produced in an electric furnace, by air mixed therewith but in the absence of water vapor,V while curve 6 shows the same effect in the presence of water vapor. Curve 'I shows the extent of oxidation of carbon monoxide in the same gaseous mixture as represented by curve 5 wherein the excess of air was 21 to 28%. Curve 8 shows the extent of the oxidation of carbon monoxide in the gaseous mixture `corresponding to curve 6 wherein the excess of air is 23 to 26%. Curve 9 shows the extent of oxidation of carbon monoxide in such a mixture in the presence of water wherein the excess of air is 97 to 99%.

In Fig. 3, curve I0 shows the extent of oxidation of elemental phosphorus in a phosphate reduction furnace gas, produced in a blast furnace, by air mixed therewith in the absence of water vapor. Curves II and I2 show the same effect in the presence of water vapor. Curve I3 shows the extent of oxidation of carbon monoxide in the gaseous mixture corresponding to curve I0 wherein the excess of air is 85 to 100%. Curve I 4 shows the extent of oxidation of carbon monoxide in the gaseous mixture corresponding to curve I I wherein the excess of air is 84 to 88% vand curve I5 shows the extent of the oxidation of carbon monoxide in the gaseous mixture corresponding to curve I2 wherein the excess air is 84 to 98%.

One example for the operation of the present invention is given for the preferential oxidation of elemental phosphorus in a phosphate furnace gas from an electric furnace. A mixture of the electric furnace gas and air was made by admitting 202 cubic feet of air into 94 cubic feet of the furnace gas per hour per cubic foot of enclosed oxidation zone just prior to the admission of the gas into said zone. The temperature within the zone was indicated by a thermocouple and maintained constant at 436 C. by admitting atomized water into the air as it was admixed with the gas, the amount of water being regulated by a magneticvalve in the conduit supplying the water, actuated by the thermocouple in the oxidation zone. An analysis of reaction products leaving the' zone showed a conversion of 99.96 per cent of the 'elemental phosphorus admitted thereto into phosphorus pentoxide and a conversion of 5.8 per cent of the carbon monoxide to carbon dioxide. The above operation corresponds to the oxidation of 2.3 pounds of elemental phosphorus per hourper cubic foot of space in the enclosed zone or 6.7 cubic feet of elemental phosphorus vapor per hour per cubic foot of enclosed zone and the amount of air corresponds to 12'9 per cent of the theoretical amount of oxygen required for the oxidation of the elemental phosphorus in the electric furnace gas to phosphorus pentoxide.

Another example for the operationof the present invention is given for the oxidation of elemental phosphorus in phosphate reduction fur- Ai mixtureoff'the naces gas fromf a blast. furnace. blast: furnace gas: was; made by admitting 237 cubic feet of air-into 945 cubic feet-,ot the furnace gas per hour per cubic foot offenclosed; oxidation zonejust prior tor-the admission of gas into said zone., The temperature wit-.hinl the zone Wasfindi'cated: by' tlflermocouple and* maintained' at 577 C. byadmitting atomized water into theair'after it was admixedA with the-gas the amount of water being regulatedf by a4 magnetic valve in the conduit supplying the water; actuated'v by. the thermocoupleinthe oxidation: zone. An analysis of a. reaction product leaving the zone showed aiconversion of 100% ot the elementall phosphorus admitted thereto;v into; phosphorus; pentoxide and a conversion, of 4.7 per cent ofthe carbon monoxide.` into; carbon dioxide. The; aboveY operation corresponds to the. oxidation ot 2;3 poundsl of elemental phosphorus per hour per cubic; foot: of space in the enclosedi zone or 6i7i cubic` feetV of elemental phosphorus vapor: per hour per: cubic footof enclosed zone and theamount of air cor.- responds to 148 per cent. ofthe theoretical amount of oxygen required for the oxidation of elemental phosphorus ini the blast furnace gas to-` phosphorus pentoxide.

It is evident that there are numerous factors which Will influence conditions for the most satisfactoiy operation of the present invention the actual limits of which cannot be established except by a specific application to each raw mate,- rial, the specific apparatus used and the character of the nal products required.

This invention is directed primarily to thepreferential oxidation of elemental phosphorus in phosphate reduction furnace gases such as pro.. duced either in an electric furnace or in a blast furnace. The invention is, however, not limited to application With gases which alone have cornpositions typical of electric furnace or blast furnace gas. In other words, a small or substantial portion of the elemental phosphorus may be condensed from an electric furnace gas andthe residual gas therefrom treated to obtain a preferential oxidation of the phosphorus remaining therein.

Air is the oxygen-containing gas most readily adaptable and ordinarily used for the purpose of oxidizing elemental phosphorus. The amount of air used should in any event correspond tothetheoretical oxygen requirement for combining with all of the elemental phosphorus to form phosphorus pentoxide and, in order that the reaction may be carried to completion at a practical rate, it is desirable to have a small excess of oxygen above that theoretically required. However, in the case of the oxidation ofy phosphorus in electric furnace gas, this excess of oxygen should not exceed 50 per cent of theorywhile in the blast furnace gas this excess should not exceed 250 per cent of theory. Experience to date indicates that an excess of to 40 per cent of oxygen is preferable when using electric furnace gas and an excess of 50 to 100 4per, cent. is preferable when using blast furnace gas.

The gas containing elemental' phosphorus and the required amount of air is uniformly mixed at a regulated rate and passed into an enclosed zone where the mixture is maintained at apredetermined temperature. Since thereactionbetween the elemental phosphorus and oxygen is exothermic, provision must be made. to, remove heat in order that such regulated temperature will not be exceeded. This may bel accomplished by the; indirect' cooling of the` encl'osedzone,4 by re-.-

turning: some or the residual gasrom: the: exit-vof the enclosed zone into. the'. inlet of: the. enclosed zone aifter the phosphorus pentoxideitherein has been removed: andl the. residual gas' cooled; somewhat, oir-by atomizing the cooling liquid intoithe inlet of thei enclosed: zonev thereby utilizing its latent: heat of vaporization'. 'I'his latter method of: cooling is particularly adaptable in. thisl instance through. theuse. of water as the presence offwater in` vapor formV is inV certaink instances. desirable for combinationV 'withthe phosphorus pentoxide inv ordere that the hydrated.y phosphorus pentoxide maybe separated from` the eflluentgas as phosphoric. acid.. The amount of. waterre'- duiredv will dependA not only upon. the.n thermal characteristics of. the. apparatususedbutthelteme perature: Whiclris maintained in-,the enclosed oxidation zone,Y withlowertemperatures requiring; the use of4 morewater than that required at, a. higher temperature. Amounts of water between 4.52 and 1-2 pounds per pound of phosphorus oxidized have beenf used` satisfactorily forthis. purpose;

The temperatureewhich isrequired to beimaintained inthe enclosed oxidation, zone isf of the or;- der of 500 C. The application` of suchv a temperature makes it,possiblev to obtain a. substantially complete oxidation, of all of the, phosphorus to phosphorus pentoxide and still; have only a very small proportion of the-carbon monoxide associated' therewith oxidized to carbon dioxide. The optimum'temperature will vary somewhat depending upon the character of the. mixture in whichthe oxidation takes'place, with the higher concentration of,I elemental phosphorus in such a mixturerequiring a slightly lower temperature than that required where. the gaseous. mixture contains a very small proportion of'- elemental phosphorus such as that existing when blast furnace gas is: mixed with the requisite amount ofV rEhe oxidation; of;r phosphorus in such a gas-V air. eous mixture: begins to take place readily at temperatures as low as200" C., and increases rapidly to temperatures of the order of 100-to 800 C.`

tionof the phosphorus pentoxide formed by the carbon monoxide. present. Therefore, it appears that While the temperature of the order of 500 C. is generically critical, a temperature between 400 and 500 C. is preferable where high concentration` of elemental phosphorus is present suchas in gaseous mixtures produced by the use of elec.- tric furnace gas while temperatures of theorder of 450 to 550 C. are preferable when using-gaseous mixtures of lower concentration of elemental phosphorusy such as. obtained by the use of gas of the character of blast furnace gas.

ciated therewith. Expressedin other terms, this corresponds, to '7 cubic feet of elemental phos.

phorus vaporv per hour, per cubic foot` ofl enclosed zone-or the passage. of a. mixture. 'of electridiurnace gas containing 7 per cent elemental phosphorus and air containing a 50 per cent excess oxygen at the rate of 350 cubic feet of the mixture perhour per cubic foot of enclosed zone or a mixture of blast furnace gas containing 0.7 per cent of elemental phosphorus and air containing a 200 per cent excess of oxygen at the rate of 1500 cubic feet per hour per cubic foot of space in the enclosed oxidation zone. The volumes referred to are on the standard temperature and pressure basis.

A study of the preferential oxidation of elemental phosphorus in mixtures containing a consderable proportion of carbon monoxide has been made over a considerable range of conditions, including a considerable temperature range, various amounts of excess oxygen in the oxygen-containing gas used and varying amounts of water vapor present. To show both the extent of oxidation of phosphorus to phosphorus pentoxide and the corresponding extent of oxidation of carbon monoxide to carbon dioxide, examples of the results obtained using electric furnace gas under specific conditions are shown in Table 1 and illustrated in Fig. 2.

cent elemental phosphorus vapor which comprises (a) forming a uniform gaseous mixture of said electric furnace gas and an amount of air containing an excess but not more than per cent excess of oxygen required to combine with the elemental phosphorus to form phosphorus pentoxide; and (b) maintaining said gaseous mixture uniformly at a temperature of about 500 C.

2. A process of preferentially oxidizing all of the elemental phosphorus and not more than a small proportion of the carbon monoxide in a phosphate reduction furnace gas from a blast fur nace containing in the order of 0.7 to 0.8% of elemental phosphorus which comprises (a) forming a uniform gaseous mixture of said blast furnace -gas and an amount of air containing a substantial excess but not more than 250 per cent excess of oxygen required to combine with the elemental phosphorus to form phosphorus pentoxide; and (b) maintaining said gaseous mixture -uniformly at a temperature of about 500 C. for a suicient length of time to oxidize substantially all of the phosphorus to phosphorus pentoxide and not more than a small proportion .25 of the carbon monoxide in said mixture.

Table I-Oridatzon of elemental phosphorus and carbon monoxide in electric furnace gas as a function of temperature Percent theoretical Exilt gas, Tempera- Oxida- CO oxivo Ime Curve number ture hot Air to H, O to tion to dized to percent zone, C. give form Pz0t% C 02% P205 HP O3 C0 0| 50o 121 0 9s. 1 2.2 s2. 9 4. 1 601 12B 0 99. 8 3. 5 30. 0 4. 5 702 122 0 100. 0 14. 6 28. 7 0. 9 901 125 0 95. 0 31. 0 23. 3 0. 4 472 126 102 98. 7 4. 3 32. 8 3. 6 701 124 102 100. 0 22. 4 2G. 4 0. 0 903 123 101 74. 0 21. 2 0. 1 470 199. 102 99. 6 10. 1 19. 6 5. 5 702 197 100 100 o. 0 7. 6 1. 3

Other examples of the results obtained using blast furnace gas under specic conditions are shown in Table 2 and illustrated in Fig. 3.

Table Z-Omidation of elemental phosphorus and carbon monoxide in blast furnace gas as a function of temperature Percent theoretical Exilt gas,- Tempera Oxida- CO oxi- V0 me Curve number ture hot Air to H2O to tion to dized to percent' zone, C. give form PzO5% C 0 1% P205 HP O3 C O Og phosphate reduction furnace gas from an electric furnace containing of the order of 7 to 8 per cent elemental phosphorus which comprises (a) forming a uniform gaseous mixture of said electricfurnace gas and an amount of air containing approximately 20 to 40 per cent excess of the amount of oxygen required for the conversion of the phosphorus therein to phosphorus pentoxide, (b) passing said gaseousmixture through an enclosed zone at a rate up to approximately 350 cubic feet per hour per cubic foot of space in said zone, and (c) maintaining said gaseous mixture oxygen required for the conversion of the phosphorus therein to phosphorus pentoxide, (b) passing said gaseous mixture through an enclosed zone at a rate up to approximately 1250 cubic feet per hour per cubic foot of space in said zone,

and (c) maintaining said gaseous mixture in said zone uniformly at a temperature between 450 and 550 C.

5. A process of preferentially oxidizing phosphorus in gaseous mixture containing a substantial proportion of carbon monoxide which com prises (a) forming a uniform gaseous mixture of said elemental phosphorus and carbon monoxide with an oxygen containing gasto supply oxygen in substantial excess of the oxygen required to combine lWith the elemental phosphorus therein to form phosphorus pentoxide, and (b) maintainingr said gaseous mixture uniformly at a temperature between 400 and 600 C.

GEORGE L. FREAR.l 

